The ultrafine ZnFe2O4, MnFe2O4, and cation deficit Zn−Mn ferrites were obtained by thermal decomposition of appropriate mixed complex compounds with acetylacetone (2,4-pentadione) ligands ([M(AA) x ]) at 500 °C. In ZnFe2O4 cation distribution is partially inverse with 14% of Zn2+ ions at octahedral 16d sites, while MnFe2O4 is a normal spinel. Cation distribution in nonstoichiometric (Zn,Mn,Fe)3 - δO4 (δ = 0.18−0.30) is found to be (Zn x Mny□ε)8a[Fez□ν]16d, with a random distribution of vacancies. Nonstoichiometry in Zn−Mn ferrites is accompanied by a cation valence change, i.e., partial oxidation of Mn2+ to Mn4+. Microstructure size-strain analysis shows isotropic X-ray line broadening due to the crystallite size effect and anisotropic X-ray line broadening due to the crystallite strain effect. In binary ferrites anisotropic X-ray line broadening due to the strain effect is higher in ZnFe2O4 than in MnFe2O4, while in ternary cation-deficient Zn−Mn ferrites it decreases as the vacancy concentration δ increases.

Spherical shaped nanoparticles of series Y(2 - x)Eu(x)O(3) (x = 0.06, 0.10, 0.20, and 2) and Gd(2 - x)Eu(x)O(3) (x = 0.06, 0.10) were prepared by thermolysis of 2,4-pentanedione complexes of Y, Gd, and Eu. The bixbyite phase of Gd(2 - x)Eu(x)O(3) samples was formed at 500 degrees C, whereas the thermal decomposition of Y and Eu complexes' mixtures occurred at higher temperatures. Linearity in the concentration dependence on lattice parameter confirmed the formation of solid solutions. The distribution of Eu(3+) in Gd(2 - x)Eu(x)O(3) was changed with thermal annealing: in the as-prepared sample (x = 0.10) the distribution was preferential at C(3i) sites while in the annealed samples, Eu(3+) were distributed at both C(2) and C(3i) sites. Rietveld refinement of site occupancies as well as emission spectra showed a random distribution of cations in Y(2 - x)Eu(x)O(3). The photoluminescence (PL) measurements of the sample showed red emission with the main peak at 614 nm ((5)D(0)-(7)F(2)). The PL intensity increased with increasing concentration of Eu(3+) in both series. Infrared excitation was required to obtain good Raman spectra. The linear dependence of the main Raman peak wavenumber offers a non-destructive method for monitoring the substitution level and its homogeneity at the micron scale.

In this paper we report results of structural, spectroscopic, and magnetic investigations of MgFe2O4 nanoparticles prepared by soft mechanochemical synthesis. MgFe2O4 nanoparticles crystallize in Fd3¯m space group with mixed cation distribution and reduced percentage of Fe3+ at tetrahedral (8a) sites. Discrepancy in the cation distribution compared to that in the bulk Mg–ferrite is one of the highest known. X-ray line broadening analysis reveals crystallite size and strain anisotropy. The saturation magnetization, Msat=62 emu/g measured at 5 K is twice higher than that found in the bulk counterparts. Such high value of Msat is attributed to the low value of cation inversion parameter (δ=0.69), to the core/shell structure of the nanoparticles and to the surface/volume ratio. Mössbauer spectrum collected at room temperature reveals ferrimagnetic ordering between Fe3+ ions in 8a and 16d sites, while zero-field-cooled (ZFC) and field-cooled (FC) M(T) measurements were shown superparamagnetic state above 350 K.

The results on the synthesis, microstructure, structure and DC magnetization studies of nanocomposite Zn,Ni ferrite/NiO powder obtained by thermal decomposition of acetylacetonato complexes are reported in this paper. According to the results obtained by inductively coupled plasma optical emission spectroscopy (ICP-OES) element analysis and multiphase Rietveld refinement, the three samples made are composed of spinel-ferrite (86.7%–96.7%) and NiO (3.3%–13.3%) phases. The compositions of the spinel-ferrite (SP) phase in the investigated samples, S1–S3, are Zn0.72Ni0.24Fe1.98O4, Zn0.56Ni0.29Fe2.07O4 and Zn0.40Ni0.40Fe2.10O4, respectively. Due to the cation deficiency in spinels, created vacancies induce a partial change in the cation valence, . The vacancy distribution is found to be random at 8a and 16d cation sites, except in sample S3, where all vacancies are over octahedral sites. The x-ray line broadening due to crystallite size effect is found to be isotropic for all spinels, while the x-ray line broadening due to the strain effect is anisotropic. A correlation between the Zn2+ occupancy of the tetrahedral site and the 650 cm−1 Raman peak intensities is shown. The observed coercivity decrease and shift in hysteresis loop in the samples are caused by the interaction between spinel and NiO phase. The results of M(H) measurements point to the properties of an ensemble of interacting nanoparticles. High saturation magnetization values and superparamagnetic behaviour at room temperature point to the technological significance of the title compounds.

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We present a study of the structural and magnetic properties of (Mn,Fe) 3-d O 4 nanoparticles synthesized by soft mechanochemistry using Mn(OH) 2 Â 2 H 2 O and Fe(OH) 3 powders as starting compounds. The resulting nanoparticles with a composition of the (Mn,Fe) 3-d O 4 type are found to have a core/shell structure with different Mn/Fe ratios in the core and at the surface. XPS analysis points to valences of þ2, þ3, and þ4 for Mn and þ3 for Fe at the particle surface. Combined results of XRPD, Mössbauer spectroscopy, and EDX analysis suggest that there is a deviation from stoichiometry in the nanoparticle core compared to the shell, accompanied by creation of cation polyvalence and vacancies. The value of saturation magnetization, M S , of 73.5 emu/g at room temperature, is among the highest reported so far among nanocrystalline ferrite systems of similar composition. V C 2012 American Institute of Physics. [http://dx.

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